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CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Vol. III - Microreactors - T. Illg, V. Hessel MICROREACTORS T. Illg Institut für Mikrotechnik Mainz GmbH, Carl-Zeiss-Strasse 18-20, 55129 Mainz, Germany V. Hessel Eindhoven University of Technology, Den Dolech 2, 5600 MB Eindhoven, The Netherlands Institut für Mikrotechnik Mainz GmbH, Carl-Zeiss-Strasse 18-20, 55129 Mainz, Germany Keywords: microreactor, micro processing, process intensification, microchemical engineering Contents 1. Introduction 2. General benefits of microreactors 3. Selected types of microreactors 3.1. Liquid / Liquid Contactors (Micromixers) 3.1.1. Lamination and Hydrodynamic Focusing 3.1.2. Jet Mixing 3.1.3. Split-and-Recombine Mixing 3.1.4. Recirculation-Flow Mixing In Curved Channels 3.1.5. Recirculation-Flow Mixing In Bas-Relief Mixers 3.1.6. Barrier-Embedded Micromixer 3.1.7. Microreactor with Integrated Mixer 3.1.8. Gas/Liquid Contactors 3.1.9. Falling Film Microreactors 3.1.10. Taylor- and Annular Flow Reactors 3.1.11. Packed Bed Microreactor 3.2. Catalytic Gas-Phase Microreactors 4. Selected examples of use 4.1. Liquid/LiquidUNESCO Reactions – EOLSS 4.1.1. Selective Friedel-Crafts Aminoalkylation 4.1.2. Alkylation 4.1.3. Nitration with High-Energetic Nitrating Agents 4.1.4. LithiationSAMPLE CHAPTERS 4.1.5. Selective Oxidation 4.1.6. Beta-Peptide Synthesis 4.1.7. Radiolabeled Imaging Probe Generation 4.2. Gas/Liquid Reactions 4.2.1. Halogenation 4.2.2. Hydrogenation 4.3. Catalytic Gas-Phase Reaction 4.3.1. Epoxidation 4.3.2. Partial Oxidation ©Encyclopedia of Life Support Systems (EOLSS) CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Vol. III - Microreactors - T. Illg, V. Hessel 5. Cost analysis 6. Eco efficiency analysis 7. Process safety Glossary Bibliography Biographical Sketches Summary Microreactors open a novel way of chemical synthesis in a highly controlled way. Due to their improved mass and heat transfer, these devices are well suited, e.g., for mixing-sensitive, fast and highly exothermic reactions. Endothermic reactions profit as well from the improved thermal management. This leads to a better exploitation of resources and decrease of energy consumption of chemical processes and will hereby increase their costing and eco-efficiency. An additional interesting benefit is the enabling to run reactions in a safe way under unconventional process parameters known as new process windows. This includes processing at unusually high temperatures and pressures - high-p-T processing. In this overview, selected examples from the diversity of microstructured components are given and grouped by their scopes of applications. This comprises first microreactors or micromixers for liquid / liquid contacting, followed by microdevices for gas / liquid contacting and then by catalytic gas-phase microreactors. 1. Introduction This chapter gives a review of the different types of microreactors, their benefits and their usage in chemical engineering. First, general characteristics of microreactors are discussed [37] - excellent mass and heat transfer, safety issues, diffusion transport etc. - in the following, different types of reactors are presented and some examples of use are going to be shown. Then, important aspects for industrial application, like cost analysis, eco-efficiency analysis and process safety, will be shortly discussed. In the last years, great efforts have been undergone to carry out reactions at small scale. These undertakings led to the field of Micro Process Technology, which includes the concept of doingUNESCO chemistry in a different way– byEOLSS improving and intensifying existing processes. Microreactors are typically continuous systems and the microstructure dimensions have to be small enough to provide the necessary heat transport and mass transfer. The prefix “micro” relates to the inner life of the reactor and not to the components thatSAMPLE are build around. CHAPTERS There is a wide range of manufacturing techniques from established methods that stem from microelectronics [1, 4, 5] up to modern ultra precision engineering and micro erosion techniques [1, 6, 7]. These versatile techniques allow a large variation of accessible microreactor materials such as steel, metals, silicon, ceramics, etc. as well as the lab material classes polymers [1, 8, 9] and glass [1, 10]. The main argument for using microstructured components in a chemical process is process intensification [37]. This subsumes first of all order-of-magnitude changes in ©Encyclopedia of Life Support Systems (EOLSS) CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Vol. III - Microreactors - T. Illg, V. Hessel conversion and selectivity or increased space-time yields, but is more and more used in a broader definition addressing also waste reduction, energy savings and better safety. Totally, this means having much increased performance at the same reactor footprint or, vice versa, shrinking down the reactor dimensions [11]. The preferential way for the usage of such microstructured components is to implement them into a running process at the point where they are needed or where their benefits can intensify the course (plant retrofit approach). 2. General Benefits of Microreactors There are several benefits of microstructured reactors [12, 37]. The usability of microreactors for highly exothermic reactions is based on their large surface / volume ratio. Thereby, the heat, which is generated by the reaction, can be transferred very efficiently out of the system. This avoids hot spots and the formation of side products, as e.g. evident from coloration of the product. Besides, endothermic reactions can be heated up to reaction temperature more efficiently than in conventional batch vessels. Another benefit is to achieve small characteristic lengths for transport of matter in the range of a few ten to less than a micron, which accelerates the diffusion transport so that operation under intrinsic kinetic conditions can be achieved. This makes microstructured reactors well suited for very fast reactions, even when being mixing sensitive. Industrial reactors have typically an interface / volume ratio of some 10 m2 m- 3 up to 100 m2 m-3. Conventional lab-scale apparatus comprise typically a few 100 m2 m-3 and in a few cases have at best 2000 m2 m-3. Opposed to this, the surface / volume ratio for microstructured elements is very large up to 20000 m2 m-3 and higher. Thus, microreactors are ideal tools for multi-phase reactions, e.g. to work under kinetically controlled conditions while keeping the conversion rate at maximum. An additional benefit of these small devices is the very low inner volume, which is important for process safety, e.g. to limit the damage potential for worst-case scenarios in case of a process upset. The exact defined and short residence times in such systems make it possible to optimize selectivity and space-time yield. 3. Selected TypesUNESCO of Microreactors – EOLSS When categorized by the presence of the phase(s) involved, microreactors can be subdivided further by the types of contacting principles typically employed as first step to initiate reactionSAMPLE by mixing. Thus, micr oreactorsCHAPTERS are grouped here for contacting liquid and liquid, gas and liquid or gas and gas phases. In the following, a few examples stemming from such classes are given to exemplify the diversity of microreactors for the different applications. 3.1. Liquid / Liquid Contactors (Micromixers) A large number of mixers with different mixing principles are available for contacting liquids and liquids. Pure mixing tasks are, e.g., given for making disperse liquid / liquid systems such as emulsions or dispersions. Mixing has to be combined to reaction for ©Encyclopedia of Life Support Systems (EOLSS) CHEMICAL ENGINEERING AND CHEMICAL PROCESS TECHNOLOGY – Vol. III - Microreactors - T. Illg, V. Hessel single-phase or multi-phase organic systems. If the reaction demands more time than provided by the mixing chamber (which is common), delay loops such as tubes or capillaries are added to the system for completing the reaction. Alternatively, a micro heat exchanger-reactor may follow the mixer in case of higher demands on heat transport. If a catalyst is required for the reaction, the simplest approach is to fill tubes or chambers in microdevices with powders or particles. A more advanced and tailored way of catalyst provision, however, is the coating of the channel walls, e.g. by slurry, spraying, sol-gel or vapor deposition techniques. Some micromixers with different mixing principles are shown in Figure 1. Their special mixing principles are going to be explained in the following sub-sections. Figure 1: A: Interdigital mixer for diffusion mixing, B: Nozzle (“Star Laminator”) mixer for jet mixing, C: Bas-relief (“Caterpillar”) mixer for recirculation (convective) mixing (medium and high Reynolds numbers) and split/re- combination mixing (low Reynolds number), D: Impinging jet mixer for collision mixing via jets. (by courtesy of IMM). 3.1.1. Lamination and Hydrodynamic Focusing Lamination means reduction of fluid distances to an extent that diffusion on its own becomes effective (under laminar-flow conditions). Hydrodynamic focusing, typically done by geometric constraints, is a simple means to further reduce the characteristic dimensions. In this way, mixing times in order of milliseconds and below can be achieved. Laminated streams are easily parallelized (multi-lamination) by grouping several inlet channels or nozzles. In a typical interdigital micromixer